Process for breaking petroleum emulsions using certain hydroaromatic analogues of certain hydrophile hydroxylated synthetic products



- ters or weak brines.

Patented Nov. 13, 1951 OFFICE PROCESS FOR BREAKING PETROLEUM EMULSIONS USING CERTAIN HYDRO- AROMATIC ANALOGUES OF CERTAIN HYDROPHILE HYDROXYLATED SYN- THETIC PRODUCTS Melvin De Groote, St. Louis, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Application December 10, 1948, Serial No. 64,443

invention is a continuation in part of three of our copending applications, Serial Nos. 726,201 and 726,204, both filed February 3, 1947, (both now abandoned), and Serial No. 8,722, filed February 16, 1948 (now Patent No. 2,499,365, dated Mar 7, 1950).

: One specific aspect of our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil," roily oil, emulsified oil. etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft wa- Controlled emulsification and subsequent demulsification under the conditions just mentioned are of signficant value in removing impurities, particularly inorganic salts, from pipeline oil.

Demulsification as contemplated in the present application includes the preventive step of commingling the demulsifier with the aqueous component which would or might subsequently become either phase of the emulsion in the ab- 'sence of such precautionary measure. Similarly, such demulsifier may be mixed with the hydrocarbon component.

Briefly stated, the present process is concerned with the breaking or resolving of petroleum emulsions by means of certain alicyclic compounds which are, in turn, derived from the specified synthetic resins. The ultimate compounds, are, in turn, the oxyalkylated derivatives, i, e., the polyhydric derivatives of such resins. For convenience, subsequent reference to present process refers to the breaking of petroleum emulsions as diiferentiated from the process of making the herein specified chemical compounds which. may be used for demulsification as well as for otherpurposes. A 1 q "Hie-present process is concerned with breaking 20 Claims. (Cl. 252-331) 2 petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of certain'hydroaromatic analogues of oxyalkylated thermoplastic phenol aldehyde resins as hereinafter described. As will be pointed out subsequently, such hydroaromatic analogues are obtained by conversion of an arcmatic compound by hydrogenation. Such hydrogenation can be applied to the resin prior to oxyalkylation or can be applied to the oxyalkylated resin. The resins as initially prepared are aromatic derivatives in so far that they are resins of the phenol-aldehyde type.

More specifically then, the present process i concerned with breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to hydroaromatic analogues of certain hydrophile hydroxylated synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, and (B) an oxyalkylation-susceptible, fusible, organic solvent-soluble, water-insoluble, phenol-aldehyde resin; said -resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula consisting of ethylene radicals,propylene radi cals, butylene radicals, hydroxypropyleneradi cals, and "hydroxybutylene radicals, and is'a numeral varying from Ito-20; withthe roviso droxylated derivative; Part 4will be concerned 1 with the hydrogenation of the resin: Part 5 will be concerned with the oxyethyl'ation of'the hydrogenated resin; Part 6 will be concerned withthe use of such hydroaromatic hydrophile hy-- droxylated derivatives as demulsifiers.

PART .1

As to the preparation of the phenol-aldehyde resins, reference is made to our co-pending applications, Serial Nos. 8,730 and 8,731, both filed February 16, 1948 (both now abandoned}. In such co-pending applications we described. a.-.i fu sible, organic solvent-soluble, water-insoluble resin polymer of the formula on: V on on R IR "11 In such idealized representation n" isa numeral varying. from 1 to 13 oreven more, provided that the resin is fusible-and organic solvent-soluble. R is a hydrocarbon radical having at least 4 and not over 8 carbon atoms. 'Intheinstantapplication. R may have as many as 12 carbon atoms, as in the case of a resin obtained. from a dodecylphenol. In theinstantinvention it may be first suitable to describe the-alkylene oxides employed as reactants, then. the aldehydes, and finally the phenols, for the reason. that the latter require. a more elaborate description- The alkylene oxides which may be. used are the alpha-beta oxideshaving not more than 4 carbon atoms, to wit, the alpha-beta ethylene oxide, alpha-beta propylene-oxide, alpha-beta butylene oxide, glycide, and methylglycide.

Any aldehyde capable. of forming. a methylol or a substituted methylol group and having not more than 8 carbon atoms is satisfactory, so long as it does not possess some other functionalgroupor structure which will conflict with the: resinification reaction or with the subsequentoxyalkylation of the resin, but the use of formaldehyde, in its cheapest form of anaqueous solution, for the production of the resins is particularly advantageous. Solid polymers of formaldehyde are more expensive and higher aldehydes are both less reactive, and are more expensive. 'Furthermore, the higher aldehydes may undergo other reactions which are not. desirable, thus introducing difficulti s into the: rcsinification step. Thus and a comparable product prepared from the same phenolic reactant and heptaldehyde on the other hand. The former, as shown in certain subsequent examples, is a hard, brittle, solid,

whereas the latter is soft and tacky, and obviously easier to handle in the subsequent oxyalkylation procedure. p Cyclic aldehydes may be employed; particularly The employment of furfural rebenzaldehyde. quires careful control for the reason that in addition to its aldehydic function, furfural can form vinyl condensations by virtue of its unsaturated structure; 7 final for-'useinpreparing products from the presentprocessmost conveniently conducted with V weak alkaline catalysts and often with alkali metal carbonates... Useful aldehydes, in addition to formaldehyde, are acetaldehyde, propionic aldehyde, butyraldehyde, Z-ethylhexanol, ethylbutyraldehyde; heptaldehyde, and benzaldehyde, turfural and glyoxal. It would appear that the useof glyoxal should be avoided due to the fact .acetaldehyde, for example, may, undergo an-aldol condensation, and it and most of the higher aldehydes enter. into self-resinification when treated that it is tetrafunctional. However, our experience has been that, in resin manufacture and particularly as described herein,apparently only one of the aldehydic functions enters into the resinification reaction-.- The inability of the other aldehydic function to enter into the reaction is presumably due ,tdstearic hindrancef Needless to say, one canuse a mixture'of two or more aldehydes-althoughusually this hasno advantage. a

Resins of the kind-whichar'e used as intermediates in this invention are obtainedwith-the'use of acid catalysts or alkaline catalysts, or without the-use of any catalystat all, Among the useful alkaline catalystsare ammonia, amines,- and quaternary ammonium bases. It 'is' generallyiaccepted that when, ammonia. and amines-areemplayed as catalysts they enter into the I conderk sation reaction and, in fact, may operate by initial combination with the. aldehydic reactant. The compound 'hexamethylenetetramine illustrates such a combination. In light of these various reactions it becomes difficult to. present any formula which would depict the structure of the various resins prior to oxyalkylation. 'Morewill a be. said subsequently as to thedifference between the use: of an alkalinev catalyst and an acid catalyst; even in the use of an alkaline catalystthere I is considerable evidence to indicate that the products are not identical where different basic materials are employed. The basic materialseme ployecl include not only those previously. enumerated but also the hydroxides. of. the alkali metals, hydroxides of thealkal-ine earth metals, salts of strong bases. and weakacidssuch as sodium acetate, etc. a

Suitable phenolic reactants include the ,following: Paraetertiaryrbutylphenol;. paraes'econdary-butylphenol; para-tertiary-amylphenol.; parasecondary amylphenol; paraetertiaryhexylphenol;v para-isooctyl-phenol; ortho-phen? ortho-benzylylphenol; para-phenylpheriol; phenol; para-benzylphenol; and para-cyclohexylphenol, and the corresponding ortho-para substituted metacresolsand 3,5-xylenols. Similarly, j one may use paraor ortho-nonylphenol or. a. 7 'mixture, paraordecylphenol or, a mixture,

or .para- '01 ortho-dodecylr,

menthylphenol, I phenol. .1

For convenience, the-phenol. has previously; been referred t as-monocyclicfin order to. differ; T entiate; from fusednucleus polycyclic.phenols, 5 .1911 asfiubstituted. naphthols. Specifically}.

The zproduction of resins from fur- 1monocyclic is limited to the nucleus in which -ithe'hydroxyl radical is attached. Broadly speaking, where a substituent is cyclic, particularly .aryl, obviously in the usual sense such phenol is actually'polycyclic although the phenolic hy- 1droxyl is not attached to a fused polycyclic nu- :following formula:

hydrogen atoms and hydrocarbon radicals having at least 4 carbon atoms and not more than 12 6 large interfacial area. Once the reaction starts to a moderate degree, it is possible that both reactants are somewhat soluble in the partially reacted mass and assist in hastening the reaction. We have found it desirable to employ a small proportion of an organic sulfo-acid as a catalyst, either alone or along with a mineral acid like sulfuric or hydrochloric acid. For example,

\ alkylated aromatic sulfonic acids are effectively carbon atoms, with the proviso that one occur- 'rence of R is the hydrocarbon substituent and the other ,two occurrences are hydrogen atoms, and with the further provision that one or both of the 3 and 5 positions may be methyl substituted.

:"'-' Ih'e above formula possibly can be restated more conveiently in the following manner, to wit, that the phenol employed is of the following formula, with the proviso that R. is a hydrocarbon is'ubstituent'located in the 2,4,6 position, again with the provision as to 3 or 3,5 methyl substitution. This is conventional nomenclature, numbering the various positions in the usual clockwise manner, beginning with the hydroxyl position as one:

' The manufacture of thermoplastic phenolaldehyde resins, particularly from formaldehyde and a difunctional phenol, i. e., a phenol in which one of the three reactive positions (2,4,6) has been substituted by a hydrocarbon group, and particularly by one having at least 4 carbon atoms and not more than 8 carbon atoms, is well known. As'has been previously pointed out, there is no objection to a methyl radical provided it is present inthe 3 or 5 position.

Thermoplastic or fusible phenol-aldehyde resins are usually manufactured for the varnish trade and oil solubility is of prime importance. For this reason, the common reactants employed are butylated phenols, amylated phenols, phenylphenols, etc. The methods employed in manufacturing such resins are similar to those employed in the manufacture of ordinary phenolformaldehyde resins, in that either an acid or alkaline catalyst is usually employed. The procedure usually differs from that employed in the manufacture of ordinary phenol-aldehyde resins in that phenol; being water-soluble, reacts readily with an aqueous aldehyde solution without further difiiculty, while when a water-insoluble phenol i employed some modification is usually adopted to increase the interfacial surface and thus cause reaction to take place. A common sglvcnt-is-sometimes employed. Another procedurel employsrather severe agitation to create a salt plus a small quantity of strong mineral acid, as shown in the examples below. If desired, such organic sulfo-acids may be prepared in situ in the phenol employed, by reacting concentrated sulfuric acid with a small proportion of the phenol. In such cases where xylene is used as a solvent and concentrated sulfuric acid is employed, some sulfonation of the xylene probably occurs to produce the sulfo-acid. Addition of a solvent such as xylene is advantageous as herein after described in detail. Another variation of procedure is to employ such organic sulfo-acids, in the form of their salts, in connection with an alkali-catalyzed resinification procedure. Detailed examples are included subsequently.

Another advantage in the manufacture of the thermoplastic or fusible type of resin by the acid catalytic procedure, is that, since a difunctional phenol is employed, an excess of an aldehyde, for instance formaldehyde, may be employed without too marked a change in conditions of reaction and ultimate product. There is usually little, if any, advantage, however, in using an excess over and above the stoichiometric proportions for the reason that such excess may be lost and wasted. For all practical purposes the molar ratio of formaldehyde to phenol may be limited to 0.9 to 1.2, with 1.05 as the preferred ratio, or sufiicient, at least theoretically, to convert the remaining reactive hydrogen atom of each terminal phenolic nucleus. Sometimes when higher aldehydes are used an excess of aldehydic reactant can be distilled 011' and thus recovered from the reaction mass. This same procedure may be used with formaldehyde and excess reactant recovered.

When an alkaline catalyst is used the amount of aldehyde, particularly formaldehyde, may be increased over the simple stoichiometric ratio of one-to-one or thereabouts. With the use of alkaline catalyst it has been recognized that considerably increased amounts of formaldehyde may be used, as much as two moles of formaldehyde, for example, per mole of phenol, or even more,

with the result that only a small part of such aldehyde remains uncombined or is subsequently liberated during resinification. Structures which have been advanced to explain such increased use of aldehydes are the following:

Such structures may lead to the production of cyclic polymers instead of linear polymers. For

for such resins.

this reason, it has been previously pointed out larly with vacuum, may be in the neighborhood of 175 to 250 C., or thereabouts. 7

It may be well-to point out, however, that the amount of formaldehyde used may and does usually aifect the length of the resin chain. Increasing the amount of aldehyde, such as formaldehyde, usually increases the size or molecular weight of the polymer.

In the hereto appended claims there is specifled, among other things, the resin polymer containing atleast 3 phenolic nuclei. Such minimum molecular size is most conveniently determined 7 as a rule by cryoscopic method using benzene, or some other suitable solvent, for instance, one of those mentioned elsewhere herein as a solvent As a matter of fact, using the procedures herein described'or any. conventional resinification procedure will yield products usually having definitely in excess of 3-"nu clei. In other words, a resin having an average of 4, 5 or 5%; nuclei per unit is apt to. be formed as a minimum in resinification, except under certain special conditions where dimerization may occur.

However, if resins are prepared at substantially higher temperatures, substituting cymene, tetralin, etc, or some other suitable solvent which boils or refiuxes at a higher temperature, instead of xylene, in subsequent examples, and if one doubles or triples the amount of catalyst, doubles or triples the time of refluxing, uses a marked excess of formaldehyde or other aldehyde, then the average size of the resin is apt to be distinctly over the above values, for example, it may average 7 to 15 units. Sometimes the expression 7 lowstage resin or low-stage intermediate is employed to mean a stage having 6 or 7 units or even less. In the appended claims we have used low-stage to mean 3 to 7 units based on average molecular weight. a

The molecular weight determinations, of course, require that the product be completely soluble in the particlar solvent selected as, for instance, benzene. The molecular weight determination of such solution may involve either the freezing point as in the cryoscopic method, or,

less conveniently perhaps, the boiling point in an ebullioscopic method. The advantage of the ebullioscopic method is that, in comparison with the cryoscopic method, it is more apt to insure complete solubility. One such common method to employ is that of Menzies and Wright (see J. Am. Chem. Soc. 43, 2309 and 2314 (1921).). Any suitable method for determining molecular Weights will serve, although almost any procedure adopted has inherent limitations. A good method for determining the molecular weights of resins, especially solvent-esoluble resins, is the cryscopic procedure of Krumbhaar which employs diphenylamine as a solvent (see Coating and Ink Resins, page 157, Reinhold Publishing Co. 1947).

' Subsequent: examples will i'llust-rate'the' use of anacid catalyst, an alkaline catalyst, and.-no catalyst. As far as resin mnufacture per sods concerned, we prefer to use n acid catalyst, and

particularly a mixture of an organic sulfa-acid and a mineral acid, along with a suitable solvent, suchas xylene, as hereinafter illustrated inde tail. However, we have obtained products from resins obtained by use of an alkaline catalyst which were just as satisfactory as those obtained employing acid catalysts. Sometimesa combing-A tion of both-types of catalysts is used indifferent stages of resinifioation. 'Re sins so'obtainedare also perfectly satisfactory.

In numerous instances the higher molecular weight resins, i. 'e., those referred to as high-stage resins, are conveniently obtained by subjecting 7 lower molecular weight resins to vacuum distillation and heating. Although such procedure sometimes removes only a modest amount or event 7 perhaps nolow polymer, yetit. is-almostcertam to produce further polymerization. For instancp.

acid. catalyzed resins obtained in the usual-man:

ner and having a molecular weight. indies-fins the presence of approximately 4 phenolic-units or'thereabouts may be subjected to suchtreat.-

ment, with the result that one obtains a resin, having approximately double 7 this molecular The usual procedure is, to use a sec.- 1 ondary-step, heating the resin in thepresenceor weight.

absence of an inert gas, including steam. 'ot by use of vacuum. V 4 1 i We have found that. under the usual conditions of resinification employing-wphenolsof the kind here described, there is little or no tendency-to form binuclear, compounds, 1. e., dimers, resultin from the combinatiomior example, of 2"mo1esof a phenol and one mole of formaldehyde, particurlarly where the substituent has 4 or Scarbon atoms. Where the number of carbon atoms in a substituent approximates the upper limit specified herein, for instance '2 or 8, there may be some tendency to dimerization. The usual procedure to obtaina dimer involves an enormously large excess of the phenol, for instance, 8 to 10 moles mole of aldehyde.

herein.

Although any narily' employed may be used in the manufacture of the herein contemplated resins or; for that, matter, such'resins may be purchased inthe; open market, We haveIfound it particularly desirable to use the procedures described elsewhere herein, 7 a and employing a combination of anorganicsulfol acid anda mineral acid as a catalyst, and'xylenc as a solvent. .By way. of illustration, certain sub i sequent examples are included; but it. is tor-be Y understood the herein described inventionis not the subsequent oxyalkylation thereof.

suitable manner.-

I'kYIatiQnL which is, the preferred reaction. depends; oncon tact between a non-gaseous phase and a gaseous phase; It can, for exampl'e, be carried out bymelting the thermoplastic resin and subjecting-it to; treatment with ethylene oxide-or the likaiorby' treating a suitab-lesolution orsuspension. Since thernelting-ipoints of the resins; are often h ig'hct than 'desired iri the initialfstage of oxyethylatiem Substituted; dihydroxydiphenylmethanes obtained from substi tuted phenols are not resins asthat terms. is;

conventional procedure ordie' V particularly oxyethylation we have found it advantageous to use a solution or suspension of thermoplasticresin in an inert solvent such as xylene. Under such circumstances, the resin obtained-in the usual manner is dissolvedby heatingin xylene. under a reflux condenser or inany other suitable manner. Since xylene or an equivalent inert solvent is present or may be present duringloxyalkylation, it is obvious there is no ob-jectionto having a solvent present during the resinifying stage if, in addition to being inert towards the resin,v it is also inert towards the reactants and also inert towards water. Numerous solvents,.particularly of aromatic or cyclic nature, are suitably adapted for such use. Examples of such solvents are xylene, cymene, ethyl benzene, propylbenzene, mesityv-v lene, decalin (decahydronaphthalene), tetralin gtetrahydronaphthalene), ethylene glycol diethylether, diethylene glycol diethylether, and tetraethylene glycol dimethylether, or mixtures of one 'or more. Solvents such as dichloroethylether, or dichloropropylether may be employed either alone or in mixture but have the objection that the chlorineatom in the compound may slowly combine with the alkaline catalyst employedin oXyethylationQ Suitable solvents may be selectedfromthis group for molecular weight determinations H I V The use'of such solvnts'is a convenient expedient in the manufacture of the thermoplastic resins, particularly since the'solvent gives a more liquid reaction mass and thus prevents overheating, and also because the solvent can be employed in connection with a reflux condenser and a water trap to assist in the removal of water of reaction and also water present as part of the formaldehyde reactant when an' aqueous solution of formaldehyde'is used. Such aqueous solution, of course, with the ordinary product of commerce containing about 37 to 40% formaldehyde,

is the preferred reactant; When such solvent is used it is advantageously added at'the beginning of the resinification procedureor before the reaction has proceeded very far.

The solvent can be removed afterwards by distillation with or without the use of vacuum, and

a finaI higher temperature can be employed to complete reaction if desired. In many instances his most desirable to permit part of the solvent,

particularly when it is inexpensive, e. g., xylene, to remain behind in a predetermined amount so as to have a resin' which can be handled more conveniently in' the oxyalkylation stage. If a more expensive solvent, such as decalin, is employed, xylene or other inexpensive solvent may be added after the removal of decalin, if desired.

In preparing resins from difunctional phenols it is common to employ reactants of technical grade. The substituted phenols herein contemplated are usually derived from hydroxybenzene.

As a rule, such substituted phenols are comparatively free from unsubstituted phenol. We have generally found that the amount present is considerably less than 1% and not infrequently in v the neighborhood of of 1%,. or even less. The

amount of the usual trifunctional phenol, such as hydroxybenzene or metacresol, which can be tolerated is determined by the fact that actual cross-linking, if it takes place even infrequently, must not be sufiicient to cause insolubility at the completion of the resinification stage or the lack ofhydrophile properties at the completion of the oxyalkylation stage. T a

The exclusion of such trifunctional phenols as hydroxybenzene or metacresol is not based on th'ezfactthat. the mere random or occasional inclusion .of an unsubstituted phenyl nucleusin the resinmolecule or in one of several molecules, for. example, markedly alters. the characteristics of the oxyalkylatedderivative. The presence of aphenyl radical having a reactive hydrogen atom available or having a hydroxymethylol or a substituted hydroxymethylol group present is a. potential source of. cross-linking either during resinification or oxyalkylation. Cross-linking leadseither. to insoluble resins or to non-hydrophilic. products resulting from the oxyalkylation procedure: With this rationale understood, it is obvious that trifunctional .phenols .are tolerable only. in a minor .proportionand shouldnot be presentto theextent that insolubilityis produced in theresins or that the productresulting from oxyalkylation isgelatinous, rubbery, orat least nothydrophile. As tothe rationale of-resinification,. note particularly what is said hereafter in differentiating between resoles, Novolaks, and resins obtained solelyfrom difunctional phenols.-

Previousreference has been made to the fact that. fusible. organic solvent-soluble resins are usually linearbut maybe cyclicwSuch more complicated structure may beformed, particularly ifaresin prepared in the usual manner is converted into a higher stage resin by heat treatmentin vacuum as previously mentioned. -This again is areason for avoiding any opportunity for cross-linking due to the-presence of any appreciable amount of trifunctionalphenoh- In other words, the presence of-such reactant may cause cross-linking in aconventional resinification procedure, or in the oxyalk-ylation procedure,- or in the heat and vacuum treatment if it is employed as part of resin manufacture. Our routine procedure in examinin -a phenol for suitability for preparing products -to be used in practicing the invention is to prepare a resin employing formaldehyde in excess (1.2-moles of formaldehyde per mole of phenol) and usingan acid catalystin the manner described hereinafter in. Example la. If the resin so obtained is .8017 vent-soluble in any one of the aromatic or other solvents previously referred to, it is then subjected to oxyethylation. During .oxyethylation a temperature is employed of approximately to C. with addition of at least 2 and advan-v tageously up to 5 moles of ethylene oxide per phenolic hydroxyl. The oxyethylationis advantageously conducted so as to require from afew minutes up to 5 to 10. hours. If theproduct so. obtained is solvent-solubleand self-dispersing or emulsifiable, or has emulsifying properties, the phenol is perfectly satisfactory from the stand,- point of trifunctional phenol content. The solvent may be removed prior to the dispersibility or emulsifiability test. When a product becomes rubbery during oxyalkylation due to the presence of a small amount of trireactive phenol, as previously mentioned, or for some other reason, it may become extremely insoluble, and no longer qualifies as being hydrophile as herein specified. Increasing the size of the aldehydic nucleus, for instance using heptaldehyde instead of formaldehyde, increases tolerance for trifunctional phenol.

The presence of a trifunctional or tetrafunctional phenol (such as resorcinol or bisphenol A) is apt to produce detectable cross-linkin and insolubilization but will not necessarily do so, especially if the proportion is small.' Resinification involving difunctional phenols only may also produce'insolubilization, although this seems to be an anomaly or a contradiction of -'-What is some- II timsxsaidin regard to resinification'reactions in;- volving" difunctional phenolstonlyl This isapree sumablydueto cross-linking- This. appears. to. he. contradictory to what one might expect in light of :the theory of functionality .in resinification.

Ittis: true that undertordinary circumstancesfor.

rather under the circumstances of conventional resin: manufacture, the procedures employing .di-. functional phenols are very apt to, and almost invariablydo, yield solvent-soluble, fusible resins.

Howevenwhen conventional procedures are em:

played, in ,connection with resinsfor varnish manufactureor the like, there is involved the matter of color, solubility in oil, etc. When. resins of thesame type are manufactured for the herein contemplated 1:1urpose,.i..e., as.av raw material to be. subjected .to oxyalkylation, such criteria of selection ,are ;not longer pertinent. Stated .anotherway, one. may use more drastic conditions of resinification than those. ordinarily employed tozmoduce resins for the present purposes. Such more drastic conditions of 'resinification may in; clude. increased amountsof .catalyst,'higher tem- Peratures. longer time of reaction, subsequent reaction involving .heat alone or in combination with vacuum, etc. Therefore, one .is not only concerned with, the resinification reactions which yield the bulk of ordinary resins from difunct onal phenols but also. and particularly withthe V reactions. of ordinary resin manufacture which are. of importance in the present invention for the reason that. they occur under more drasticconditions of resinification which may be employed adva t eously. at t m s. and th y a well, fPhenoplasts, chapter 2. These, investigators limited much oftheir work to reactions involving. phenols having two or less reactive hydrogen atoms. Much of what appears in these most recent and most up-to date investigations is pertinent to the present invention insofar that much of it. is referring 'toresinification involving' difunctional phenols. r r

For the moment, it may be simpler to consider a most-typical type of fusible resin and-forget for .the time that such resin, at least under certain circumstances, is susceptible to further complications. Subsequently in the text it will'be pointed out that cross-linking or reaction with excess formaldehyde may take place even with one of such most typical type resins. This point is made for the reason that insolubles must be avoided in order to obtain the products herein contemplated for use as demulsifying agents;

The typical type of fusible resin obtained" from a para-blocked or ortho-blocked phenol is clearly differentiatedjfrom the Novolak type or resole type of resin; Unlike the resole type, such typical typepara-blocked or ortho-blocked phenol resin may be heated indefinitely Without passing, into an infusible stage, and in this respect is similar to a Novolak. Unlike the Novola k type the addition of a further reactant, for instance, more aldehyde, does not-ordinarily alt r u b y o e di unc i a phe nl a dee hydetyr resin; but; such addition to a. Novolak;

' causes; .cross-dinking virtue ofi thef availabi third functional position. 1

it ,What has;- beenjsald immediately preceding issubject to. modification in. this respect 2. rItis well known, forexaniple, that. dn'unctional phenols, for instance,v paratertiaryamylphenoL. v and an aldehyde, particularly formaldehyoegm'ay,

yield" heatehardenab'le resins, at least under certain conditions, as for example the use of two. moles lofformaldehyde to oneof phenoLalong I Withanalkaline catalyst". This'peculiar hardening or curing or-cross-linking of resins obtained" from difunctionalphenols has been recognized by various authorities. 1 a 7, 7 r l The compounds herein used must be hy'drophile or"'sub-surface--active or surface'active as here? inafter described, and thi'sfprecludes the forma tion of insolubles during resin manufacture or thesubsequent stage of resin manufacturewhere' heat'al'one; or heat'and vacuum, are employed, 7 In "itsor in the oxyalk 'ylation procedure. simplest. presentation the rationale of 'res'inificaf tion involving formaldehyde, for example, and.

adi'functional phenol would not be expected to form cross-links' '=However, crosselinking some times occurs and'it may-reach the objectionable" 7 stage; However, provided that the preparation of resins simply takes into cognizance the presentknowledge of' the subject, and employing preliminaryyexploratorly routine examinations'as herein indicated, thereis not the slightestdim cultypreparing'a very large number of resins of various types andfro n variousreactants, and.

by means'of different catalysts bydifferent pro-.-

cedures; all of which are eminently'suitable for the herein describedypurpo'se.

.- Now returning to. the thought, that cross- 5 linking can take place, even. wh n Clifu'nctional phenols are used exclusively, attention is di-' rected to theifollowin'gi. Somewhere during thecourse o s n manufacture there ma be a potential cross-linking combination formedfbut actual cross-linking may not take place until the subsequentstage is reached,i.'e., heat and vacuuni stage, or ,oigyalkylation stage. ,This situa f tionmay be. related orexplained in. terms of a theory .offiaws, .or Locker'stellen: which is em( ploye'd'in explainingflow-forming groups due to the fact that a ICHzOI-I radical and H atonrmay not lieinthe, same plane in the manufacture of I r ordinary phenol-aldehyderesins. Secondly, thefoif'f ation or'absence of formation' of isolubles may be related to the, aldehyde used and the ratio of aldehyde, particularly.

formaldehyde, insoraptnat a slight variation may, under circumstances not understandable,

produce insolubilizatiofi. The formation of the insoluble resin'isapparently very sensitivetothe quantity offojrmaldehyde. employedand a slight increase in the. proportion of formaldehyde may lead to. the formation of i-nsoluble gel lumps. The cause of insoluble resin formation is not clear, and nothing isiknown as to the'structure of these I fSifl's.

. All thath'as been'said previously herein as re: gard's resini'fication hasiavoided the specific r'ef-} erence to activity of a methylene hydrogen atom.

nctuallythcre isaipossibility that'under some dra t ccond ons c s i kin m take. p a thro gh rmald hyde a d t n t th m th ne b i e, Q o e ot er-reacti i vol i g a et y ene hydrogen atom.

;.-:; :inallr hereiis some evidence-that, alth u h the meta pos i sjlareanot ordinarily reactive, V

13 possibly at times methylol groups or the likeare formed at the meta positions; and if this were the case it may be a suitable explanation of abnormal cross-linking.

Reactivity of a resin towards excess aldehyde, for instance formaldehyde, is not to be taken as a criterion of rejection for use as a reactant. In other words, a phenol-aldehyde resin which is thermoplastic and solvent-soluble, particularly if xylene-soluble, is perfectly satisfactory even though retreatment with more aldehyde may change its characteristics markedly in regard to both fusibility andsolubility. Statedanother way, as far as resins obtained from difunctional phenols are concerned, they may be either formaldehyde-resistant or-not formaldehyde-resistant. 1 a V Referring again to the resins herein contemplated as reactants, it is to be noted that they are thermoplastic phenol-aldehyde resins derived from difunctional phenols and are clearly distinguished from Novolaks or resoles. -When these resins are produced from difunctional phenols and some of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is often a comparatively soft or pitchlike resin at ordinary temperature. Such resins become comparatively fluid at 110 to 165 C. as a rule and thus can be readily oxyalkylated, preferably oxyethylated, without the use of a solvent.

a. Reference has been made to the use of the word fusible. Ordinarily a thermoplastic resin is identified as one which can be heated repeatedly and still not lose its thermoplasticity. It is recognized, however, that one may have a resin which is initially thermoplastic but on repeated heating may become insoluble in an organic solvent, or at least no longer thermoplastic, due to the fact that certain changes take place very slowly. As far as the present invention is concerned, it is obvious that a resin to be suitable need only be sufliciently fusible to permit processing to produce our oxyalkylated products and not yield insolubles or cause insolubilization.

or gel formation, or rubberiness, as previously described. Thus resins which are, strictly speaking, fusible but not necessarily thermoplastic in the most rigid sense that such terminology would be applied to the mechanical properties of a resin, are useful intermediates. The bulk of all fusible resins of the kind herein described are thermo plastic. 7 v

. The fusible or thermoplastic resins, or solventsoluble resins, herein employed as reactants, are water-insoluble, or have no appreciable hydrophile properties. The hydrophile property is introduced by oxyalkylation. In the hereto appended claims and elsewhere the expression water-insoluble is used to point out this characteristic of the resins used.

In the manufacture of compounds herein employed, particularly for demulsification, it is obvious that the resins can be obtained by one of a number of procedures. In the first place, suitable resins are marketed by a number of companies and can be purchased in the open market;

in the second place, there are a wealth 'of examples of suitable resins described in the liter- The third procedure is to follow the di-- ature. rections of the present application.

v The polyhydric reactants, i. e., the oxyalkylation-susceptible, water-insoluble, organic -sol-- vent-soluble, fusible, phenol-aldehyde resins derived from difunctional phenols, used as inter-- mediates to produce the products used in aci4 cordance with the invention, are exemplified by Examples Nos. 1a through 10311 of our Patent 2,499,370, granted March 7, 1950, and reference is made to that patent for examples of the oxyalkylated resins used as intermediates.

Previous reference has been made to the use of a single phenol as herein specified, or a single reactive aldehyde, or a single oxyalkylating agent. Obviously, mixtures of reactants may be employed, as for example a mixture of parabutylphenol and para-amylphenol, or a mixture of para-butylphenol and para-hexylphenol, or para-butylphenol and para-phenylphenol. It is extremely difficult to depict the structure of a resin derived from a single phenol. When mix- For that matter, one might be producing simul-- taneously two different resins, in what would actually be a mechanical mixture, although such mixture might exhibit some unique properties as compared with a mixture of the same two resins prepared separately. Similarly, as has been sug-- gested, one might use a combination of oxyalkylating agents; for instance, one might partially oxyalkylate with ethylene oxide and then finish off with propylene oxide. It is understood that the oxyalkylated derivatives of such resins, derived from such plurality of reactants, instead of being limited to a single reactant from each of the three classes, is contemplated and here included for the reason that they are obviousvariants.

PART 2 Having obtained a suitable resin of the kind described, such resin is subjected to treatment with a low molal reactive alpha-beta olefin oxide so as to render the product distinctly hydrophile in nature as indicated by the fact that it becomes self-emulsifiable or miscible or soluble in water, or self-dispersible, or has emulsifying properties. The olefin oxides employed are characterized by the fact that they contain not over 4 carbon atoms and are selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide, Glycide may be, of course, considered as a hydroxy propylene oxide and methyl glycide as a hydroxy butylene oxide. In any event, however, all such reactants contain the reactive ethylene oxide ring and may be best considered as derivatives of or substituted ethylene oxides. The solubilizing effect of the oxide is directly proportional to the percentage of oxygen present, or specifically, to the oxygencarbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is 2:3; and in methyl glycide, 1:2. In such compounds, the ratio is very favorable to the production of hydrophile or surfaceactive properties. However, the ratio, in propylene oxide, is 1:3, and in butylene oxide, 1:4. Obviously, such latter two reactants are satisfactorily employed only where the resin com- 1s position is such as to make incorporation of the desired property practical. In other cases, they may-produce marginally satisfactory derivatives,.

or even unsatisfactory derivatives. They are usable in conjunction with the three :more favorable alk-ylene oxides in all cases. 'For instance, after one or several propylene oxide orbutylene oxide molecules have been attached to the resin molecule, oxyalkylation may be satisfactorily continued using the more favorable members ofthe class, to produce the desired hydrophileproduct. Used alone, these two reagents may in some cases fail to produce sufiiciently hydrophile derivatives because of their relatively low'oxygencarbon ratios.

Thus, ethylene oxide is much more effective than propylene oxide, and propylene oxide is more effective than butylene oxide. Hydroxy propylene oxide (glycide) is more effective than propylene oxide. Similarly, hydroxy butylene oxide (methyl glycide) is more effective than.

butylene oxide. Since ethylene oxide is the cheapest alkylene oxide available and is reactive, its use 'is definitely advantageous, and especially in light of its high oxygen content. Propylene oxide is less reactive than ethylene; oxide, and butylene oxide is definitely less reactive than propylene oxide. On the other hand,;glycide may reactwith almost explosive violence and must be handled with extreme care.

The oxyalkylation of resins of the kind :from which the products used in the practice of the present'invention are prepared is advantageously catalyzed by the presence of an alkali. Useful alkaline catalysts include soaps, sodium acetate, sodium hydroxide, sodium methylate, caustic potash, etc. The amount of alkaline catalyst usually is between 0.2% to 2%. The temperature employed may vary from room temperature to as high as 200 C. The reaction may be conducted with or without pressure, i. e., from zero pressure to approximately 200 or even 300 pounds. gauge pressure (pounds per square inch). general way, the method employed is substantially the same procedure as used for oxyalkylation of other organic materials having reactive phenolic groups.

In a.

Itmay be necessary to allowfor the acidity of a resin in determining the amount of alkalinecatalyst to be added in oxyalkylation. :For' instance, if a nonvolatile strong acid .such as sulfuric acid'is usedxto catalyze :the resinification reaction, presumably after being converted into asulfonic acid, it may be necessary and is usually advantageous to add an amount of alkali equal stoichiometrically to such acidity, and include added alkali over and above this amount 'as'the' alkaline catalyst.

It isadvantageous to conduct the oxyethylation in presence of an inert solvent SuchJas xylene;

final product used as a demulsifier, it -is our. preference to use xylene. This is particularly true in the manufacture of products from lowstage resins, i. e., of 3 and up to and including 7 units per molecule.

If a xylene solution is used in anautoclave as hereinafter indicated, the .pressure readings of course represent total pressure, that is, the combined pressure duev t0 xylene and also 'due to ethylene oxideor'whatever other 'oxyalkylating agent is used. Under @such circumstances itmay be necessary at times to use substantial "pressures toiobtaineffective results'.-f or instance, pressures? up to 300 pounds along with correspondingly high temperatures, if required.

However, :even :in the instance of high-melting resins, ra solvent such as xylene can be eliminated:

in either one of= two ways: After the introductioni of approximately 2 :or- 3- moles of ethylene oxide, for example, per phenolic nucleus, there is a definitedrop in the hardness and melting pointiof the resin. At this .stage, if xylene or a similar solvent has-been added-,yit can be eliminated by distillation (vacuumdistillation if desired) and the subsequent intermediate, being comparatively-1 represents the original resin' dissolved-in propyl ene oxide-tor :butylene oxide, or a mixture which includes rtheoxyalkylatedproduct, ethylene oxide is added to react with the liquid mass until hydrophile properties are obtained. 'S-ince ethyl ene oxide *iszmore reactive than propylenexoxide or butylene oxide, .the:fin'a1 product may contain someiunre'acted:propylene oxide or-buty lene oxide which-man be-eliminated by "volatilization or ,dis-- tillatiomin:anysuitable manner. 1

Attention-is:directed to the factxthat the resins herein :described :must ibe fusible or soluble vinan organic solvent; 'E'usible resins invariablyware soluble in one or more organic solvents such as;

those"mentionedelsewhere-herein. It is tof-be emphasized,.:however, "that the organic solvent employed toz indicate or assure that the resin meets this requirement .need' not be the one used in zoxyalkyla'tion. Indeed solvents which aresusceptible-ate oxyalkylation are included in this group-of :organi'crs'olvents. Examples of such sol-f: ventsrar'e alcohols and alcohol-ethers. where'a resin is soluble in an organic solvent,-

there:are'usuallyaavailable other organic solvents whichare notisusceptible to oxyalkylation, usefulforiithe oxyalkylation :step. organic solvent-soluble resin can be finely powdered,.for instance .to to '200 mesh, and V a slurry or suspension :prepared in. xylene or the i like, and subjected to oxyalkylation. The fact that the resin is soluble in an .organicsolvent or. the fact that :it is :fusible rmeans that it .consists' of separate molecules. Phenol-aldehyde resins;

of :the type herein specified possess reactive hydrioxyl :groups and are? oxyalkylation susceptible. Considerableof what issaid immediately "here-, inafter is concerned with the ability 'tovary the hydrophileproperties of the reactants iused, from minimum :hydrophile properties to maximum;-

hydrophile.j'properties. Even rmore remarkable; and equally difiicult toexplain are the versatility. and utility. of these "compounds as one ,goesirom minimum hydrophile property to ultimate maximum hydrophile iproperty. For instancepminb munr hydrophile',.property may be described roughly as'themoint wheretwo :ethyleneoxy radi However,-

In any event, '1the' aerate cals or moderately in excess thereof are introduced per phenolic hydroxyl. Such minimum hydrophile property or sub-surface-activity or minimum surface-activity means that the product shows at least emulsifying properties or selfdispersion in cold or even in warm distilled water to C.) in concentrations of 0.5% to 5.0%. These materials are generally more soluble in cold water than warm water, and may even be very insoluble in boiling water. Moderately high temperaturesaid in reducing the viscosity of the solute under examination. Sometimes if one continues to shake a'hot solution, even though cloudy or containing an insoluble phase, one finds that solution takesplace to give a homogeneous phase as the mixture cools. Such self-dispersion tests are conducted in the absence of an insoluble solvent.

When the hydrophile-hydrophobe balance is.

above the indicated minimum (2 moles of ethylene oxide per phenolic nucleus or the equivalent) but insufiicient to give a sol as described immedi-v ately preceding, then, and in that event hydrophile properties are indicated by the fact that one can produce an emulsion by having present 10% to of an inert solvent such as xylene. All that one need to do is to have a xylene solution within the range of 50 to 90 partsby weight of oxyalkylated derivatives and 50 to 10 parts by weight of xylene and mix such solution with one, two or three times its volume of distilled water and shake vigorously so as to obtain an emulsion which may be of the oil-in-water type or the water-in-oil type (usually the former) but, in any event, is due to the hydrophile-hydrophobe balance of the oxyalkylatedderivative. We prefer simply to use the xylene diluted derivatives, which are described elsewhere, for this test rather than evaporate the solvent and employ any more elaborate tests, if the solubility is not sufficient to permit the previously noted,

If the product'is not readily water soluble it may be dissolved in ethyl orv methyl alcohol, ethylene glycol diethylether, or diethylene glycol diethylether, with a little acetone added if required, making a rather concentrated solution,

simple soltest in water Allowance must be made for the presence of a solventin the final product in relation to the hydrophllepropertles of the nnal product. l'he principle involved in the manufacture of the herem contemplated compounds for use as demulsifylng agents, is based on the conversion of a hydrophobe or non-nydroph le compound or mixture of compounds into products which are distinctly hydropnlle, at least to the extent that they have emulsifying properties or are "selfemulsifying; that 18, when shaken with waterfthey produce stable or semi-stable suspensi o'ns, 'or, in the presence of a water-insoluble solvent, such as xylene, an emulsion. In demulsincation, it is sometimes preferable to use a product having markedly enhanced hydrophile properties over and above the initial stage of self-emulsifiability, although we have found that f with products or the type used herein, most elficacious results are obtained with products which do not. have hydrophlle properties beyond the stage of self-dispersibility.

More-highly oxyalkylated resins give colloidal solutions or sols which show typical properties comparable to ordinary surface-active agents. j Such conventional surface-activity may be measured bydeterminlng thesuri'ace tension and the interfacialtension against parafiin oil or the like.

At the initial and lower stages of oxyalkylation,

surface-activity is not suitably determined in "thissame manner but one may employ an emul- 'resins herein speclned, particularly in the lower for instance 40% to 50%, and then adding enough of the concentrated alcoholic or equivalent solution to give the previously suggested 0.5% to 5.0% strength solution. If the product is self-dispersing (i. e., if' the oxyalkylated product is a liquid or a liquid solution self-emulsifiable), such sol or'dispersion is referred to as at least semi-stable in thesense that sols, emulsions, or dispersions prepared are relatively stable, if they remain at least for some period of time, for instance 30 minutes to two hours, before showing any marked separation. Such tests are conducted at room temperature (22 0.). Needless to say, a test can be made in presence of an insoluble solvent such as 5% to 15% of xylene, as noted in previous examples. If such mixture, 1. e., containing a water-insoluble solvent, is at least semistable, obviously the solvent-free product would be even more so. Surface-activity representing an advanced hydrophile-hydrophobe balance can also be determined by the use of conventional measurements hereinafter described. One outstanding characteristic property indicating surface-activity in a material is the ability to form a .permanent foam in dilute aqueous solution, for example, less than 0.5%, when in the higher oxyalkylated stage, and to form an emulsion in the lower and intermediate stages of oxyalkylation.

silication test. Emulsions come into existence as a rule. through the present of a surface-active emulsifying agent. Some surface-active emulsifying agents such as mahogany soap may pro-' duce a water-in-oil emulsion or an oil-in-water emulsion depending upon the ratio of the two phases, degree of agitation, concentration of emulsifyin agent, etc.

The same is true in regard to the oxyalkylated stage of oxyalkylation, the so-called sub-surface-active stage. I The surface-active properties are readily demonstated by producing a xylene-water emulsion. A suitable procedure is as follows: Theoxyalkylatedresin is dissolved in an equal weight of xylene. Such 50-50 solution is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably suflicient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions so produced are usual- 1y xylene-in-water emulsions (oil-in-water type) Q particularly when the amount of distilled water. used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At

time, particularly in the lowest stage of oxyalkylation, one may obtain a water-in-xylene emulsion (water-in-oil type) which is apt to reverse on more vigorous shaking and further dilution with 1 water.

If in doubt as to this property, comparison with a resin obtained from para-tertiary butylphenol and formaldehyde (ratio 1 part phenol to'1.1

formaldehyde) using an acid catalyst and then followed by oxyalkylation using 2 moles of ethylweight indicating about 4 units per resin- .molecule. Such resin, when diluted with an equal 'weight'of xylene, will serve to illustrate the emulsification test;

In a few instances, the resin may not be sufficiently soluble in xylene alone but may require the addition of some ethylene glycol diethylether above a described eisewiitre n is "ufiaerswta tijet considered the e11iiii'ra lerit 'offxylene' for thefpur of this test. I I II In many cases, thereis no doubt'as to 'the press with this invention. They "dissolve i disperse in watjery and such dispersions foamreadily: With borderline cas's, i." a, those which show only incipient hydrophileor 'surface"-active' proprty' '('sub-surface activityl tests for emulsifying properties or 'self dispersibility"are useful. The fact that a reagentis' capable of'pro'ducing a; dis-- persion in water is'p'roof that it is'distinctly hy- I I Indcub'tful c'a's'e's, comparison can'be made with the butylpherim-formaldehyde resin drophile.

analog" wherein '2 moles of ethylene" cxiue"have been introduced 'foreach phenolic nucleus. I

insoluble solventnlay 'masliithpoint at which a solvent-free product onjnieredilutiorf'in a test tube exhibits self-emulsification. For" this reason? if it is desirable to determinethe appr'oxi it is'better to" eliminate the xylene or equivalent from a small portion of the reaction mixture and test such portion; In some cases, such xylenefree're'sultant mayshow initial-or incipient hydrophile"propertiesywhereas in presence of xylene such properties would not be noted. In other cases; the first objective'indication of'hydrophile properties'may be the capacity of 'them'aterial to'eiiiulsify an insoluble solvent "such asxylene.

It; to beemphasiz'edthat hydrophile properties herein referred. to'are'such'as th'ose exhibitedby incipient s'elf-emuls'ification or the presence of enceoi" absence of hydropl'iil" or surface-active characteristics irrth'e products-used in' accordance emulsifying properties and go through the I range "Elsewhe'rait' is-pointdout that an emulsifica- I said-as to the-variation'in the effectiveness of various alkylene oxides; and most particularly of all ethylene oxide,--to introduce hydrophile character, it becomes obvious that there is a wide variation in the amount of alkylene oxide employed, as long asit is'at 1east 2 moles per phenolic nucleus," for producing products useful for the' prac'tice of this invention. Another- Variation is the molecular size of the resin chain resulting from reaction between the difunctional phenol and the aldehyde such as formaldehyde. 'It is well known that the size and nature or structure ofthe resin polymer obtained varies somewhat with the conditions of reaction, theproportions of reactants, the nature of the catalyst, etc.

Based on molecular weight determinations, most of the resins prepared as herein described, particularly in the absence of a secondary heatin; "step, contain 3 to '6 or '7 phenolic nuclei with approximately 4% or 5 nucleias an-average. More drastic conditions of resinificatio'n yield rsins'of gr'eaterch'ain' length. Such'more'in tensive resinification isa' conventional prdcedure and may' b but using thef s ame'" reactants and using more drastic conditions}-otresinification' one usually;

finds that higher'inolecular weights'are indicated by higherf'melting-points' of the resins and; tendencyto decreased -solubility. fi Seewhat has beensaid elsewhere herein in regard "to a secondary step involving the heating of a :re sin with;

or without the useofvacuum;

We have previously pointed in preparing the-resin; A combination-of data-1 evenjin the presence'of'an alkaline catalyst, the

number of moles: of aldehyde, such as'formalde f hyde; inu'st'be greater than the molesfof phenol employedinorder-to introducernethylol groups in the"intermediate' stage There is 'no indication 25 that such groups appearin the'final resin if'prej pared by the use ofair'acidcatalyst, It'is pose-f sible that such groups may appear in the finished I resins prepared solely with'an alkaline catalyst;

but we have never been ablef to' confirm this fact in an examination. of a large'number ofi 'resr ins prepared by ourselves j Our preference, how-' ever, is to use an acid-catalyzed resin, particu-' larly employing a", formaldehyde-to-phenol ratio of 0.95 to 1.20. and, as'rar-as we' hav e'be en able. to determine, such resinsareiree from'methylol groups. a matter of 'factitf is probable that in a'cid c'atalyze'd 1 resinification, the methylol. structure may appear only momentarily at the very beginningmore reaction aridlin all pr'obf-U f ability is convertedatonceinto a more complexj structure during the i'r'itrniediatefstage.

One procedure which can be employed. in the use ota new resin to prepare roductsrornse in theprocess of the 'mveritian sta determine the hydroxyl value by thVe'rl'ey-Btilsing.methl ad. or its eqi'ii'valent. The resin. as such, or inthe former. a solution as-described is then treated. with ethylene oxide in preSen eof. 0.5% to; 2% of sodium? methylate as -a; catalyst step wise fashion. The conditionspj-reaction, as far time or pen cent are, concerned; are. within the range previouslydndicated; {1th suitable agitaa; tion the I ethylene, oxide,- if added molecular proportion, combines :within a I comparatively i; .short time, =forinstance-a-few minutes to 2 to 6 hours; but Linsome instance. requires as -much as-8, to 2&1 hoursr; A useful temperature range I isI-from 1-25? to-225w -C. 'Thecompletion of the reaction ,of each addition of ethylene oxide in stepwise fashionis usually indicated by-the reduction or elimination of pressure: An amount CODVBll.

iently usedforeach addition -is=-generally equivalent to a mole; or two 1 moles; of ethylene oxide per hydroxyl radical. "When the amount of ethyleneoxide'added is equivalent to: approximately 50%by' Weight' of' the original, resin; a sample is 'tested "for inoipient hyfirophile. properties by simply shaking =up water as is, orl 'afte'r "the elimination of the solvent if'a 'solvent'is present.

.The amount of ethylene oxide used to obtain a;

useful" demulsifyi'ngagentrasxa rul'e varies from '70% by weight-of theaoriginal' resin to asmuch as "five or six .iti'mes the". weight". of. the" I original resin. In thecaseofa resin-t'derived'frompara 1 tertiary butylphenol, as' 1ittle= a's =;5.0%..bytweight I II hii'oia ii aesirea, Me anin-1? weight; of course, is measured byan suitable,

. qa h -errata alkaline or acid catalyst is advantageously used, c in preparing therein. A combination of cata lysts is sometimes used in-"two" stages; for instance, an alkaline cataly st is sometimes emf II ployedin a first stag'ejfoll'owed by neutralization and addition or a small amountbf iacid catalyst" of ethylene oxide mayv give suitable solubility. with propylene oxide, even a greater molecular proportion 'is'required and sometimes a resultant of only limited hydrophile properties is obtainable. The same is true to even a greater extent with butylene oxide. The hydroxylated alkylene oxides are more effective in solubilizing properties than the comparable-compounds in which no hydroxyl is present.-

Attention is directed to the fact that'in. the

a subsequent examples reference is made to the stepwise addition of the alkylene'oxide, such as ethylene oxide. -It isunderstood, of course, there is' 'no objection to the continuous addition of allwlene oxide until the desired stage of reaction is reached. In fact, there may be less of a hazard involved and it is often advantageous to add the alkylene oxide slowly in a continuous stream and in such amount as to avoid exceeding the higher pressures noted in the various examples or-elsewhere. e

It may be well to emphasize the fact that when resins are produced from difunctional phenols and some of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is a comparatively soft or' pitch-like resin at ordinary temperatures. Such resins become comparatively fluid at 110 to1165 G385 a rule; and thus'can bereadily oxyaikylated, preferably oxyethylated, without the use of a solvent.

What has been said previouslyis not intended to suggested that any-experimentation is necessary to determine the degree'of oxyalkylation, and particularly oxyethylation. What has been said previously is submitted primary to emphasize the fact that these remarkableoxyalkylated resins having surface activity show unusual properties as the hydrophile character varies from a minimum to an ultimate maximinm One: should not underestimate the utility of any, of theseproducts in a surface-active or sub-surface-active range without testing them for demulsification. A few .simple laboratory tests which can be conducted in a routine manner will usually give all the information that is required;

. For instance, a simpleruleto follow is to prepare a resin having at least three phenolic nuclei and being organic solvent-soluble. Oxyethylate such resin, using the following four ratios of moles of ethylene oxide per phenolic unit equivslant: 2 to 1; 6to 1; 10 to 1; and to 1. From a sample of each product remove any solvent that may be present, such as xylene. Prepare 0.5% and 5.0% solutions in distilled water, as

previously indicated. A mere examination of such series will generally reveal an approximate range of minimum hydrophile character, moderate hydrophile character, and maximum hy-, drophile character. If the.2 to 1 ratio does not show minimum hydrophile character by test of. the solvent-free product, then one should test its capacity to form an emulsion when admixed with xylene or other insoluble solvent. If neither. test shows therequired minimum hydrophile property, repetition using 2 /2 to 4 moles per phenolic nucleus will serve. Moderate hydrophile character should be shown by either the'6 to 1 or'10 to 1 ratio. Such moderate hydrophile charater is indicated by-the fact that the sol in distilled water within thepreviously mentioned concentration range is a permanent translucent sol when'viewed in a comparatively thin layer, for instance the depth of a test tube.- Ultimate hydrophile character is usually shown at the 15 to -r ratio test in that -adding a smallamountof aninsoluble solvent, for instance 5% of xylene,-

yieldsa product which will give, at least temporarily, a transparent or translucent sol of the kind just described. The formation of a perma nent foam, when a 0.5% to 5.0% aqueous solu-' tion 'is shaken, is an excellent test for surface activity. Previous reference has been made to the fact that other oxyalkylating agents may require the use of increased amounts of alkylene oxide. However, if one does not even care to go to the trouble of calculating molecular weights, one can simply arbitrarily prepare compounds containing ethylene oxide equivalent to about 50% to 75% by weight, for example 65% by weight, of the resin to be oxyethylated; a second example using approximately 200% to 300% by weight and a, third example using about 500% to'750% by weight, to explore the range of hy-' drophile-hydrophobe balance. 1

A practical examination of the factor of oxyalkylation level can-be made by a very simplepounds can then be tested for solubility and, gen-- er'ally speaking, this is all that is required to give a suitable variety covering the hydrophile-hydrophobe range. All these tests, as stated, are intended to be routine tests and nothing'more. They are intended to teach a person, even though unskilled in oxyethylation or oxyalkylation, how to prepare in a perfectly arbitrary manner a series of compounds illustrating the hydrophilehydrophobe range.

-If one purchases a thermoplastic or fusible resin on the open market selected from a suitable number which are available, one might have to make certain determinations in order to make the quickest approach to the appropriate oxyalkylation range. For instance, one should know (a) the molecular size, indicating the number of. phenolic units; (22) the nature of the aldehydic: residue, which is usually-CH2; and (c) the nature of the substituent, which is usuall butyl, amyl,. or phenyl. With-such information one is in sub-- stantially thesame position as if one had per-- sonally made the resin prior to oxyethylation.

" For instance, the molecular weight of the in-' ternal structural units of the resin of the follow- (11:1 to 13, or even more) is given approximately by the formula: (Mol'. wt. of phenol 2) plus mol. wt. of methylene or substituted methylene radical. The molecular weight of the resin would be 1:. times the value for the internal limit plus the values for the terminal units. The left-hand terminal unit of the above structural formula, it will be seen, is identical with the recurring internal unit except that it has one extra hydrogen. The right-hand terminal unit lacks the methylene bridge element. Using one internal unit of a resin as the basic element, a resins molecular weight is given approximately by taking (n plus 2) times the Weight of .the internal element. Where the resin molecule has. only 3 phenolic nuclei as in the struc.-

tureeshown; this calculation ,-w,i'11: be irieifiofi-qby several .:per cent; but aslit grows largenpto contain- 6-,-,-9.; or. 12phenolicnuclei, the-formula come$:.to beamore than-satisfactory. Using-such; anapproximate weight, onev needgonly introduce, for example. two molal. weights-of ethylenegoxideor slightly more, .per phenolicpnucleus;to-;produce aproduct of minimal'hydrophile. characters g ther; .oxyalkylation gives.- enhanced; hydrgophile;

character. Although-=we-;have prep red .endnd testeda large number of oxyethylated productsaof thetype-described herein, we have found no. instance where the use of less than. 2 moles of ethyleneoxideper phenolic'nucleus gave desirable products.

7 Examples 1b through'18b,and thez-tableswhieh appear incolumns 51 through '56 of.-our..-s aid. Patent 2,499,370 illustrate .oxyalkylation products from resins which are useful as intermediates .for producing the esterified products usedin {@GKJOIIQ" anc wi z he p s tapp i tion S ch examp es giving exact and completedetails for carrying out the oxyalkyla'tion procedure.

a, The es p i t y ky ati n. Y IO XA cky. v s liqui to r rueh meltin so ids-r- Their colonva es mali ht-yellow throughgamber; to, a deep .red. or even almost, black. In the manuiacture oi resins, particularly hard-resins, as the reaction-progressessthe reaction mass frequently goes through a; liquid state to a sub-resinousqor semi-resinousstate, often characterized; by being: tacky or StiCkYp to a. final .completeresin.; .Assthe resinissubjected to oxyalkylation these same physical :changes tend-to take place in reverse. H one-starts with 4 a solidresin, oxyalkylationtends to makeit tackyor semi-resinous and further oxyalkylation makes the tackiness disappear and changes the 7 product to a liquid. .Thus, as the resin is. oxyal-lcylated-it decreases in viscosity, that is, -be-;. 40 comes more liquid or changes from a solid ;to.a q d. p cu rly when it is nv rted;to.:tl1e water-dispersible or water-soluble stage. Thecolor of the oxyalkylated derivative is usually considerably lighter than the original product from whichit is made, varying from a pale straw, color to an amber or reddish amber. The viscosityusuallyvariesxfrom that of an .oil, like castor oil, to that of athick viscous-sirup. Some products are Waxy. {Hie presence oi-a solvent, such as 15% xylene or the like, thins the viscosity considerably and also reduces the color in dilution. No undue. significance need be attached to the color for the reason that if the same compound is prepared in glass and iniron, the latter usually has somewhat darker color. ,If the resins are prepared as customarily-employed in varnish resin manufacture, i. 6;, a procedure that excludes the presence of oxygen during the resinification andsubsequent cooling of theresin, their;

of course the initial resin is much-lighter in color. Wehave employed some resins, which initially are almost water-white. and also yield lighter celoredfinal product.

.Actually, in consideringnthe ratio ofalkylene. oxide to add. and Wehave previously pointed out that this can be predetermined using laboratory tests, it is our actualfpreference from afpracti'calstandpoint to make testson' a'sm'all'pilot plant scale. make one run, andonly'one; 'andthat -we have a complete series which shows' the progressive effect: of I introducing the *oxjza-lkylating agent; for instance, the ethyleneoxy radicals. Gurp're'ferred.

procedureis as follows: -:.We ;;prepare; a; suitable; 7 whether;

e a emp m ureae a o W W aIsmtake samples at intermediate-pointsas indi 'j "Our reason for so"'doingis that We"'70".;

24 resinjworriorethali matter. purchase it n-th Z a ket. em fispo nd 65m a d. po nds-of: x lene aceplate th in'a'suitable denser. lutiom is complete. H soft e ie re-fluid emiu di a readily reparedtmv io :wa su h a th of ortho-tertiary amylpheno ho-h r-t phenyl. ontno-iiecy plienq or tbeu w his mo e l e ht e dehrdes ha iorm ldehrd u e' used. a q etwnee'd 1 0 2;. dd d'b tme v e side aa te ;e som nc 9 Qmsar,0n des r d We e ed a talystfqrw estanceV 0? .l$. i al-12992. orm-era 20%. W3 W t er. an q e; water ,of sol nor-formation, ;We then t ft them fl s conde s r and use he u m nc ut clavemman thr iei n we of fll-neu d pote y ene oxid -be ens d equivalent to 750% of the original resin. Wep

catedinfthefollowingtablez L, r

- V nd.9

- h vl n x edde Pens-p und that.

Percentage.

Oxyethylationto 750% 'can' usually be cornpleted within 30 .hours =and freq-uentl m'ore quickly I he-samples taken are rather small; forai stan'ce 2 to ouncesgso that;no-correction needfY be made. in regard to. theresidual reactionimas'sc; Each sample isdividecl intwon One-halfthe pleis placed inian eva'porating :dish iontthe steami bath; over-night so. as. r to eliminate 1, the: xylene. Then 15% solutions are:lpreparedftromi both isee'v ries ofisam'ples;i.- e.,gthelseries with'xylenepreser 1 exit and the seriesiwith xylene removed. r Mere visual: examination of. any samples-in solution may: :be I sufficient to indicate hydrophile character or surface. activity; i.: e.; the product-2 is soluble, forming azcolloidalsoL-zor the aqueous;

solution" foams or. shows; emulsifying} property. ;.All.these pr0pertiesrare related through. adsorp;

tion at theizinterface, for example', -a:gas-.liquid;in-.s

terface .ora a': liquidz-liquid interface. .-...If desired, 1.

surface-activity cam beimeasured:in v any one :of

the: .usualways using. a. D111 Nouy 'tensiometenorz, dropping:pipettes or: any: other procedure 'ior measuring.interracial; tension. Such tests are conventional .iand 'require. no f urtherz des'criptiong .compound'z-hav-ing' subesurface-activity; and; all. derived f rom the same resin and ioxyalk-ylatjed reference. has heenwmade;togthe-fact that one-;can

conduct arlaboratoryi ale test which-williir-i dica 1 Ola-R01 resini.-a1though= sohiblegirr sol- 7 Y vent, will yield an insoluble rubbery product, i. e.,

a product which is neither hydrophile nor surfaceactive, upon oxyethylation, particularly extensive oxyethylation. It is also obvious that one may havea solvent-soluble resin derived from a mixv ture of phenols having present 1% or 2% of a trifunctional phenol which will result in an insoluble rubber at the ultimate stages of oxyethylation but not in the earlier stages. In other words, with resins from some such phenols, addi:

, which may be noted in a long drawn-out oxyal-, kylation, particularly oxyethylation, which would not appear in a normally conducted reaction. Reference has been made to cross-linking and its effect on solubility and also the fact that, if

carried far enough, it causes incipient stringiness,

then pronounced stringiness, usually followed by a semi-rubbery or rubbery stage. Incipient .stringiness, or even pronounced stringiness, or

Him

even the tendency toward a rubbery stage, is not objectionable so long as thefinal product is still hydrophile and at least sub-surface-active. Such material frequently is best mixed with a polar solvent, such as alcohol or the like, and preferably an alcoholic solution is used. The point 'whichwe want to make here, however, isthis:

Stringiness or rubberization at this stage may possibly be theresult of etherification. Obviously if a difunctional phenol and an aldehyde produce a non-cross-linked resin molecule and if such molecule'is oxyalkylated so as to introduce a plurality of hydroxyl'groups in each molecule. then and in that event if subsequent etherification takes place, one is going to obtain crosslinking in the same general way that one would obtain cross-linking in other resinification reactions. Ordinarily there islittle or no tendency toward etherification during the oxyalkylation step. If it does take place at all, it is only to an insignificant and undetectable degree. However,

suppose that a certain weight of resin is treated a with an equal weight of, or twice its weight of,

.ethylene oxide. This may be done in a comparatively short time, for instance, at 150 or 175 C.

in 4 to 8 hours, or even less. On the other hand, if in an exploratory reaction, such as the kind previously described, the ethylene oxide were added extremely slowly in order to take stepwise samples, so that the reaction required 4 or times as long'to introduce an equal amount of ethylene oxide employing the same temperature ment and reach the intermediate stage of oxyalkylation as rapidly as possible and then proceed slowly beyond this intermediate stage. The entire purpose of this modified procedure is to cut .down the time of reaction 50 as to avoid etherification if it be caused by the extended time period. It may be well to note one peculiar reaction sometimes noted in the course of oxyalkylation, particularly oxyethylation, of the thermoplastic resins herein described. This effect is noted in a case where .a thermoplastic resin. has been oxyalkylated, for instance, oxyethylated, until itgives a. perfectly clear solution, even in the presence of some accompanying water-insoluble solvent such as 10% to of xylene. Further oxyalkylation, particularly oxyethylation, may then yield a product which, instead of giving a clear solution as previously, gives a very milky solution suggesting that some marked change has taken place. One explanation of the above change is that the structural unit indicated in the follow- 0 (czHcohnH r R then 'etherification might cause stringiness or a suggestion of rubberiness. For this reason if in an exploratory experiment of the kind previously I described there appears to be any stringiness or rubb ri e a it ma ,bawa l. fie p a t e experiing way where 812 is a fairly large number, for instance, 10 to 20, decomposes and an oxyalkylated resin representing a lower degree of oxyethylation and a less soluble one, is generated and a cyclic polymer of ethylene oxide is produced, indicated thus:

This fact, of course, presents no difiiculty for the reason that oxyalkylation can be conducted in each instance stepwise, or at a gradual rate, and samples taken at short intervals so as to arrive at a point where optimum surface activity or hydrophile character is obtained if desired; for products for use in the practice of this invention, this is not necessary and, in fact, may be undesirable, i. e., reduce the efllciency of the product.

We do not know to what extent oxyalkylation produces uniform distribution in regard to phenolic hydroxyls present in the resin molecule. In some instances, of course, such distribution can not be uniform for the reason that we have not specified that the molecules of ethylene oxide, for example, be added in multiples of the units present in the resin molecule. This may be illustrated in the following manner:

Suppose the resin happens to have five phenolic nuclei. If a minimum of two moles of ethylene oxide per phenolic nucleus are added, this would mean an addition of 10 moles of ethylene oxide, but suppose that one added 11 moles of ethylene oxide, or 12, or 13, or'14 moles; obviously, even assuming the most uniform distribution possible, some of the polyethyleneoxy radicals would contain 3 ethyleneoxy units and some would contain 2. Therefore, it is impossible to specify uniform distribution in regard to the entrance of the ethylene oxide or other oxyalkylating agent. For that matter, if one were to introduce 25 moles of ethylene oxide there is no way to be certain that all chains would have 5 units; there might be some having, for example, 4 and 6 units, or for that matter 3 or 'I'units. Nor is there any basis for assumingthat the number of molecules '27 'oil'the oxyalkylatingragent added to; each pisthe molecules of: the? :resin is .the same; or. different. fllhusnwheraformulae are-"given to: illustrate 1 or d'epi'ct. th'e' :oxyalkylated .ipro'ducts, adistributions .otiradicalsindicated arer tobe statistically taken.

1W have; howeverpincl-ud'ed specific. directions and specifications in regard to the totalamount Iiofi ethylene: oxide,: or total amount of any other oxyalk-ylating :agent, 2170 add;

lniregard ca-solubility"of'the'resins and'thea roxyalkylate'd "c'ompounds, 'and for that matter -derii7atives of' the lattent'the iollowingshould be tc nctedf In oxyalkylation,..any"solvent employed fishoul'dibernonireactive'to the alkylene oxide employed. Z This limitation does. not apply to solventsiuse'din cryos'copic: determinations for obvi- :ous rea'sonsl Attention i's"directed to'the "fact that various organic solvents may be employed -tozverify th'at'theresin is organic-solvent-soluble.

Sdchssolubilityz-test merely characterizes the -speed agitation; jgi've suitab In: scmecasesptlie changenom slow speed iagvitaticn; for example, in'a :laboratory auto'clave agitation with a stirrer operating; at. a speed. of '60 to 200 R; P.:.=1vr.; to high sped. agitationgwlth the stirrer operating "at 250 10. 350" n; :P.=M.; :r

duoes the time'required for oxyalk'y-lation by about one-half to'two-thi'rds' 'Frequently xylenesoluble products :which give insoluble products by procedures employing I comparatively; slow ucts" when produced "by si with high speed agitation, 1

l'ieve'; of the reduction 1 in the time required with i consequent elimination ="o' curtailment-orb ortunity for curing or getnenzauonq Even formation of'an' insoluble product is not involved,

action, thereby reducing production-time; by in- --creasin gagitating "speed In large-scale "operawhich -ar soluble in xylene or the like, rather than those which are soluble only'in' some other solvent'containing elements other than carbon and hydrogen, for instance, oxygen or chlorine. Such solvents are usually polar, semi-polar, or ,slightlyspolaroin. nature, compared ,with xylene, .cymenae etc.

r Referenceto..cryoscopicmeasurement is .concerned with'the use.oi-benzene. or other suitable (compound as asolvent Suchmethod will show .that. conventional..resinsv obtained, .for l example.

from para-tertiary amylphenol. and formaldeh-yidein presence of. an acid catalyst, .willfhavea molecular. weight .indieatingB, 4, .5 or somewhat .greaternumberof structural units per molecule. ,If more. drastic .conditions .of .resinification are employed or if such .lowestage. resin is-.. subjected v to a .vacuum distillation treatmentv as previously .-described, .one obtains a resin' of a distinctly higher .molecular weight. Any molecularweight determination used, whether cryoscopic measv.urement or otherwise-.other :thannthe conventional cryoscopic oneemploying-benzene, should be checked so as .toinsure that-it. gives consistent. values on :suchconventionahresins: as a icontrol Frequently ,all thatis necessaryto make arr-approximation nflthel molecularaweight range -is..:to..make -a comparison -with the dimer .obtain'ed by. chemical. combination .of two moles of thesame phenol, and onemole of thesame alde- -liyde .under conditions to insure dimerization. As to the preparation of dimers from substituted phenols, see .Carswell, Phenoplasts, pa e 31.

The increased viscosity, resinouscharacter, and

I decreased solubi1ity,-etc., of the higher polymers jin'comparison with the dimer, frequently are all that is required to ,establis'h that the resin-conftain's 3 or more structural units per molecule.

' Ordinarily, the oxyalk'ylationis carried out in ,giau'tdclaves provided with 'agitators'or stirring de jlfiC8S. W'have found that the speed Ofthe agijtatio'n markedly influences the time of reaction.-

ti'ons, We -have demonstratedg that ieconomical manufacturingresultsifrom continuous 'oxyalkylsuit-a enas is,- an*operation in which 'thealkylene continuously-fed"to= the reaction vessel,

with

tory operation.

Previous reference has been made to the fact that inpreparing esters or compounds of the kind herein described, particularly adapted for .demu1sific ationof water-in-oil emulsions, and

for that matter for other purposes, one should make a complete exploration of the wide varia-v tion in hydrophobe-hydrophile balance as previously referred to. It has been stated, furthermore, that this hydrophobe-hydrophile balance 1 at thenoxyalkylated resinstisiimparted, [asfan-as 40.:

extent-=.to: athe:.herein. described derivatives. This meansthat'oneemploying the present invention should take the choice of-ithemostsuitable derivative selected fromanumberfof representative :compounds thus not only should-Ha varietyof =resins. :be :zprep'ared w exhibiting -.a variety; of --oxyalkylations;:particularly -,-oxyethylations, but

the mange ct rvariation.-goes-,to-.va greater or lesser 'also'5=a'.va-1:iety: of derivatives; 1 This can be *done conveniently-in.'lightioi whathas been said .presviouslyg From apracticalI standpoint; using-pilot .zplantzequipment, for instance; an autoclave havingc-"a. .ecapacity sof: :approximately three to five gallons. .We have madel a singleirun -.by -appropriateselections in which the molalratio of resin v =equivalentzto' ethylene. oxide is one to. one, :.1 13015, '1- to 10', 1 to;'15f, andri1 :20. L'Furthermore; in making these particular runs we have" used contiriuous -addition of 'ethylen'e oxide; In the con- .tinuous'addi'tionoi ethylene oxide we-have employed, either a cylinder of ethylene oxide Withoutindded nitrogen, provided that the pressure "or. the ethylene oxide was sufflciently great to 7 'pass. into the autoclave, or else We have used ans arrangement which, .in essence, was the equivalent of .anethylene oxidecylinder withxa 1 means.-..for sinjecting nitrogen so -as-to force out thesethylene: oxidemthe mannerof, an ordinary 'seltger-bottle, combined with .themeans for either weighing. the'cylinder or: measuring the ethylene oxide-fused.:volumetricallyis' Such :procedure 7 and i arrangement for injecting liquidsiris, oi; course, convention-a1; en'ip y Such operations, as; y b0 11"continuousagitation" and taking-samplesso hydropnne prca,

the

V h sp'eed=-'ag-itation-, i. e an'agitator op- V erating -at ZSO 'to 350 R? P. "M1 Continuous oxyalkylation; other --conditions i being the same, i is -moi'e rapid thanbatch oxyalky lationflbut the laments:- ordinarilymcre convenient for labora- The foliowing idata" sheets" .ex-

he' com'binationnf I 29 as to give five difl'erent variants in oxyethylation. In adding ethylene oxide continuously, there is one precaution which must be taken at all times. The addition of ethyylene oxide must apparent by examining the columns headed Starting mix, Mix at end of reaction, Mix which is removed for sample," and Mix which remains as next starter.

30 ner described in Examples 1a through 103a of our said Patent 2,499,370, except that instead of being prepared on a laboratory scale they were prepared in 10 to 15-gallon electro-vapor heatedstop immediately if there is any indication that 5 synthetic resin pilot plant reactors, as manufacreaction is stopped or, obviously, if reaction is tured by the Blaw-Knox Company, Pittsburgh, not started at the beginning of the reaction pe- Pennsylvania, and completely described in their riod. Since the addition of ethylene oxide is Bulletin No. 2087 issued in 1947, with spe ific e invariably an exothermic reaction, whether or erence to Specification No.7l-3965. not reaction has taken place can be judged in For convenience, the following tables give the the usual-manner by observing (a) temperature numbers of the examples of our said Patent rise or drop, if any, (b) amount of cooling water 2,499,370 in which the preparation of identical or other means required to dissipate heat of reresins on laboratory scale are described. It is action; thus, if there is a temperature drop withunderstood that in the following examples, the out the use of cooling water or equivalent, or if change is One W h respect o e Si e Of the there is no rise in temperature without using Operation. cooling water control, careful investigation e S e d n e h instance s y e should b made. This solvent is particularly satisfactory for the In the tables immediately following, we are reason that it can be removed readily by distillashowing the maximum temperature nd usually tion or vacuum distillation. In these continuous the operating temperature. In other words, by e periments the sp of he st rrer in the autoexperience we have found that if the initial reclave was 250 R. P. M. actants are raised to the indicated temperature I examining the Subsequent les it Wi l b and then if ethylene oxide is added slowly, this noted that f a comparatively Small p e is temperature is maintained by cooling water until taken at each stage, for ins an e, /a to one the oxyethylation is complete. We have also inlon, one can P d through e entire molal dicated the maximum pressure that we obtained stage of 1 to l, to 1 to 20, without remaking at or the pressure range. Likewise, we have indiany intermediate stage. This is illustr t d y cated the time required to inject the ethylene ox- Examp e 04 I h r a pl s w f und it ide aswell as a brief note as to the solubilityof desirable to take a larg r s mpl f r ns n a the product at the end of oxyethylation period. 3- a 0n samp a an t rm d ate sta e. As a As one period ends it will be noted we have reresult it was necessary in such instances to start moved part ofthe oxyethylated mass to give us with a new resin sample in order to prepare sufderivatives, as therein described; the rest has ficient oxyethylated derivatives illustrating the been subjected to further treatment. All this is latter stages. Under such circumstances, of

course, the earlier stages which had been previously prepared were by-passed or ignored. This is illustrated in the tables where, obviously, it shows that the starting mix was not removed The resins employed are prepared in the manfrom a previoussample.

Phenol for resin: Para-tertiary amylphenol Date, June 22, 1948 Aldehyde for resin: Formaldehyde [Resin made in pilot plant size batch, approximately 25 pounds, corresponding to 3a of Patent 2,499,370 but this batch designated 104ml Mix Which is Mix Which Re- Starting Mix fig'g gg Removed {or mains as Next Sampl Starter Max Max Time Pressure, Temp erahrs. Solubility Lbs. Lbs. Lbs Lbs. Lbs. Lbs. Lbs. Lb Lbs. Lbs. Lb s l- Ress01- Resm6 801- Res- Sol- Res- 3 vent in vent in vent in vent in First Stage Resin'to EtO Mole] Ratio 1:1 14.25 15.75 0 14.25 15. 75 4.0 3.35 3.65 1.0 10.9 12.1 3.0 80 150 M I. Ex. No. 104b- Second Stage Resin to Et0 Molal Ratio 1:5. 10. 9 12. 1 3.0 10. 9 12. 1 15.25 3. 77 4. 17 5. 31 7.13 7. 93 9. 94 70 158 92 ST. EX. No. l05b.-

Third Stage Resin :6 Eton Molal Ratio 1:10. 7.13 7.93 9.94 7.13 7.93 19.69 3.29 3.68 9. 04 3. 84 4. 25 10.65 173 56 F8. Ex. No. l06b- Fourth Stage Resin to Et0-.. 7 h Mola] Ratio 1:15.. 3. 84 4.25 10. 3. 84 4. 25 16. 15 2.04 2.21 8. 55 1. 2.04 7. 60 220 160 )6 RS. Ex. No. 1070..." I

Fifth Stage Resin to EtO Molal Ratio 1:20.. 1. 80 2.04 7. 60 1. 80 2. 04 10.2 34; Q3. Ex. No. 108b...

I=1'.usoluble. ST-Siight tendency toward becoming soluble. FS==Fair1y soluble. RS== Readily soluble. QB =Quite soluble.

. Mix Which is Mix Which Re i Stayting-Mix figggfig of Removed [or mains as Next ,Sampie Starter 1 Max. Max. Time Prgssu e, Temp erahm Sqiqgiiity 1 .15 5.- Ifibs. gbis. 135., Lbs 'l lbls. Ifibs. Lbs l lbls. gbs.

0- es- 0- 1 es- 0- es- 0 esv vent in vent in Eto vent in Eto .vent in Eto First Stage I. Z i i 53.851!) to EtO. 1 H Moial- Ratio 1:1 0 15.0 0 15.0 15.0 3 5.0 5.0 1.0 10.0 10.0 2.0 150 "11% ST.

. Ex. No: 10%. j f v 1 Second Stage Resinto E10". I 1 f olai Ratio 1:5-. 10 10 2. 0 '10 -10 9. 4 2:72 2. 72 2. 56 7. 27 7. 27 6. 86 4,147 1 '2 f DT. ELNO. b.- j I.

Third Stage Resin to EtO H 1 1 7 Molai Ratio 1;10 7. 27 7. 27 6:86 7; 27 7.27 "13. 7 4. 16 4. 16 '7. 68 3. 15 3. 15 5.95 ..155 1% S.

No.111b j Fourth Stage .Resinto-EtO I I j r Molal Ratio 1:15. 3. 15 3.15 5. 95 3. 15 3. 15 8. 95 '1. 05 1. 05 2. 95 2. 10 2. 10 6. 00 220 1174 1 .2345 S. Ex. No. 112b Fifth Stage BesinjaEtO"; A i r 3 r MolalRatio 1:20. 2.10 2.10 6.00 1 2.- 10 2.10 8.00 i -1. "-5.220 2183 3135 118. Ex. Nq. 113b v r PhenoLfonresinfi Non'yl'phenol A'ldehydeifor tesimi'formaldehyde Date. J1me"18;'1 948 v I 5 .[Resin madeinpilotplgmt size baigpi1,.2.pppoximateiy 25 pounds, corresponding to .70ao f Patent 2,449,370, but this bgiighdesignggg lggp l V 1 BESQIpbIe. fs'laifllight tendency toward solubility. 1 T=Defi.nite tendncyioward sqi z bilitj. I fifs very isgiq e.

Phenol for resin: Para-octylphenol Aldehyde for resin: Formaldehyde Date, June 23, 24,'-1948 [Resin made in pilot plant size batch, approximately 25 pounds, corresponding to 8a of Patent 2,499,370, but this batch designated 1144.]

- i 7 Mix Which is -MixWhici1Re- Starting Mix f gggg gg of Removed ior mains as Next fia mple Starter Max Max -'-First"Stage 1 t I Resin to EtO Molai Ratio 1:1" Ex. No. 1141)...

15.8 o 14.2 15.8 3.25 3.1 3.4 0. 75 11.1 12.4 2.5 50 1112118. Second Stage Resin to EtO. Molal Ratio 1:5 11 1 Ex. No l15b llhird S taae Resin to E120- M0121 Ratio 1:10 Ex. No. 1161?...

Fourth Stage Resin to 11150.

1 i i 7. 36 0 64 7.36 15.0 120 190 1% S. I

Molal Ratio 1:15. Ex. Na. 1175....

Fifth Stage Resin to EtO Molai Ratio 1:20.

4.58 4.6 4.1 4.58 18.52 260 172 Ex..N0,.118b r Date, July 8-13, 1948 [Resin made in pilot plant size botoh,.approxi1notely;2 5 pounds, correspond,ing to 69a 01 .latgni; 2,599,319, but till; pgtendes ignotgd 1190.]

. Mix which is 1 Mix Which Rer i x gg fi g 9 Removed for. 'f mains'asNxt 1 Sample I Starterw v Mam a no 7 Pressure, Temp eraag? Solubility es- 0- es- 0- 0- esvent in vent in vvent in E- yent -in First Stage Resin to EtO. Molal Ratio'l-l Second Stage Resin to Et0'.-. M0181 Rgtio 1:5 10 Ex, No. 120b Third sum 1 I Resin to EtO...

Molal Ratio 1:10. Ex. N0. 1210"--- Fourth Stave Resin to M0,...

058,5,94 5.48 6.58 10.85 I Y v, l 00 1 60 R3455 Fifth Stage Resin to E0...

131 Ratio 1:201 Ex. No.'123b Phenol for reoin: Pam-socondary buiylphonol Aldehyde for rosin: Formaldehyde 'Date,J11ly14-15,1948 l [Re sin made in pilot plan; size batch, ap gnoxims tge ly pounds, corresponding to 2070i Patent 2,499,370, but this liatoh dsignated 1240.}

f MixWhichis li/IixWhich Re-' Starting Mix figg g gggg Removed Ior. mains as N i I mp a I'" Ma inMax v l Pressure Temp eragg Solubility Lbs: Lbs'. Lbs Lbs. Lbs. '15 Lbs. Lbs: Lbs." 'Lbsr 'g' y- Solligs- Eto Sol- Bes gf nsob Res- F .Sol- Resvent vent "in vent; I in Y'nt m FirstStahe 7 g Resin to Et0 v M0181 Ratio 1: 14.45 15. 0 14.45 15. 55 4. 25 5.97 6.38 v 1.75 8.48 9.17 2.50 150 M2 N5. Ex;N0. 124b Q I h ,7

Second Stage Resin to EtO Molal Ratio 1:5. 8 48 fEx. No. 125b Third Stage Resin to EtO- Molal Ratio 1. Ex. ,No. 12615.

Fourth Stage Resin to Et0 }4.82 5.18 4.82 5.18 LL25 V I 400 183 S.

Molal Ratio 1:15

4.15 0 3.85 4.15 11.0 v ;.)0 Vs. Fifth sum" Resin to EtO Molal Ratio 1:20.

Phenol for resin: Para-tertiary amylphenol Aldehyde for rein} Furfufal.

Dgte, naw-31,1945 I v r .7 [Resin made on pilot plant size-batch, approximately! pounds, correspondingto 42otPatent 2,499,370, but.thisbatchdeignatedasliiflj I Mix which Mix 771113115111 Starting Mix, I iggg gg Removed'lo't mainsasNxt I Sample Stanter. Mar M .w

7 Time I ,lfressure, Temgeya; Solubihty gbis. I bs. Lbs gb s. "Jim. 1 .11 5. 11 t s. l bs. i -"4 L I es- 0- es: oes: II *0,- es-J 1 vent in want 111 Etc went in .Eto. .vent. m.

First-Stage Resin to Etc-F" 4 I .I. t f .17. Molal Ratio 121-. 11.2 18 0 11 2 13 0 3 5 2 75 4 4 0. 85 8 13 5 2 120 135 -Notsolublo. Ex.No. 13412.-." I I 7 Second Stage 7 Resinto:Et0-

57 WT I w i i i I I Molal Ratio 1:5" 8.45 13.6 2. 8.45 13.6 12.65 5.03 8.12 7.55 3.42 5.48 5.10 150 M murmur.

Ex. No. 13545.. 5 soluble.

Third Stage ResintoEtO...-. 3 I r I T}? v, M0181 Ratio 1:10 14.5. 8.0 4.5, 8.0 14.5 2.45 4. 35 7.99 2. 05 3.55 6.60 180 I 163 i m M "Sblubl'm? Ex. No. 136D..- I

Molal Ratio 1:15 5.48 5.10 3.42 5.48 15.10 I 180 188 wry-soluble. EX. N0. 1375...-.- 5

Fifth Stage 1 Resmm-Etm.-- g' I 1 M0181 Ratio 1:20.- '2. 05 3.65 6.50 2.05 3.65 13.35

EX. N0. 1385;-"

Phenol fair-resin. -Mehthgjl Aldehyde or resin; Furfural.

Date, Sept. 23-24, 1948 '[Resin made on'pilot size bateh, approximately 25 pounds, corresponding to 89a of Patent 2,499,370 but this batch designated as 13911.]

Mix Which is 'Mix Which Re- Starting Mix i g g g Removed for mains as Next 9 Sample Starter Max Max Time 4 lgressure, gemp erthrs solublllty Y 5 s.sq.1n. ure 52?: 52;: egg- 52?: 112:: gg- 52?: 522: egg- 525' 522: 5 vent in vent in vent in vent .in 1

"'"j"i;azgaz'-".""' "'1' 'H" Resin to EtO I V MolalRatiolzl 10.25 17.75 p 10.25 17.75 2.5 2.65 4.60 0.65 7.5 13. 1.85 90 V .150 l .55 Not soluble Ex;N0.'139b 1. T. T .I p

Second Stage .Resin to EtO .Mo1al.-R atio1:5.. 7.6 13.15 1.85 7.6 13.15 9.35 5.2 9.00 6.40 2.4 4.15 2.95 80 177 g }6 Somewhat .Ex.No..1 b V my I I 59mph. 17lirdStooe Resin to EtO- 1 f Mplal Ratio 1: 4 22 6.98 4.22 90 165 y. Solubleq -Ex.Ne.;1 1b U .:v .7

Fourth Staoe i Rosin to Et0 Mo1a1 V p 100 I 171 .Verysoluble.

2 95 90 v 150 Verysolnble.

i Pamoctyl Aldehyde for es z'n: Furfural Date, October7-8, 1948 x I [Resinmade on pilot plant size batch. approximately 25 pounds, corresponding to 42a of P atent 2,499,370 with 206 parts bv weight of commercial para-oetylphen'ol replacmg 164 parts by weight'of para-tertiaryamylphenol'but this batch designated as 144a.]

' Mix Which is Mix Which Re- Starting Mix Removed for mains as Next .1, I Sample Starter Max. Max. i "Pressure, 'Temperagg Solubility V lbs. sq. in. tune, C.

Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Sol- Res- $2; $01: Resg g? Sol- Res- $5 801- Res-' Egvent in vent i'n vent in vent in First Stage Resin to EtO. v M i =1 MolalRatio 12-1.. 12.1 18.6 12.1 18.6 5 3.0 5.38 S. 28 1. 34 6. 72 10.32 1.66 80 P 150 1 M2 Insoluble. Ex. No. 144b H ;S'econd,Stage Slight tend- Resin'to' EtO... 5 MolalRatlo lzin 9.25 14.25 9.25 14.25110 3.73 5.73 4.44 -5.52- 8.52-6.56 --l00 I 177 1 942 Ward be- Ex'.No;;'145b comingsoluble Third Stage V I Resin 5 51500-- r M6181 Ratio 1:10.- -72 10. 32 1. 66 6. 72 10. 32' 14. 91 4. 97 7. 62 -11. 01 r 1. 4 2. 70 4 3. i Y -85 v 182 V4 Fairly solu- Ex.N0.-1'46b ble.

Fourth Stove Resinto EtO l, v Q 'Molal Ratio 1:15-. 5.52 8.52 "e. 56 5.52 8.52 -19.81 w 100 I '176 if: Readil sol- Ex. No. 14711... ub1e.-- I

Fifth Stage ResintqEtO.. '-'M0lal Ratio 1:20.. 175 2.70 3.90 1.75 '2. 70 8.4 5 -80 I M Q te S0 1 Ex. No. 148b '-ble.

1 Resin to mom. i

955374;.538: 3.9 g 4.0 Phenoljjo'r. resin-x Bdrap hemjl. Aldehydejorrfeaim, Eurfziral Date, October 11-13,194s [Resin-made on pilot lant size batch; apptoximatelyfipounds; correspondiugmodzaofifatant esevamwitmlzopmt byweightotmmmq tcial pamp enylphenol replacinglfipamsby weightot para-.tertiaryamylphenol buhthis batchdesignated $1490.], 1

r i mwmch-is-.-. wanton-net. Starting Mix i g'gg gg Removedton mains as Next 1 1 Sample. Starter: n e V: p Z .lr essnre, Temp era Solnbllity Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. -Lbs; Lbs: t Sol- Res- $3 sot-'- R'es-.. $3 Sol-1 1125+, Egg" tsol-z Rest ,52%, vent in.. ,vent .in. .vent in. nut in. t

First Stage Reslnto:EtI.... L w Molal Ratio 1 13 9 16.7 13.9 16.7 3.0 3.50 7 4.25v 0.80 10. 35' 12.45 2.20 100i 100'} Ex. No. 1495.

Second Stage Resin'toEtOnn 1 3 M0121 Ratio 1:5... 12. 2.20 10.35 12. 45 12.20 5.15 6.19 6.06 5.20 6.26 6.14 801 183 Ex. No. 150b.

Third Stage Resin'to Et0-. v v v a 1 i Molal Ratio 1:10. '8 90 10.7 8.90 10.70 19.0 5.30 6.38 11. 32 3.60 4.32 7.68 V 90 193 u lairlyysolci- Ex.No.151b-- Fourth Stage .ReSintOiEtOL. H 1' i. I Molal Ratio 1:15. 6 20 6.26 6.14 5.20 6.26 16.64 '100' .RGIGHIIIOI- Ex.N0. 152b- 311119. v

Fifth Stage Resi'ntoiEtU" r" v Sample-somewhat mbberyandgelat 3 58 3.oo 4.32 7.68 3.60 4.32 15.68 mousbuflamysolumm 230, 170 a,

Phenol for res in: Para-nonyl'ph'enol Aldehyde f6? resin: Filrfural V Date, October 13 15, 1948 I r V r 7 p g I [Resin made on'pilot plant sizebateh; approximately ziponnds. .oorrespondmmto-mtofyatent z flmambut thisabatchtdesignated' as 154a].

, Mix Whichtis: 1 Mixwmcmm. figg ffggr Removedion: '2 mainsns'Next.

Sample: 7 Starter" Max Bream-e,- -Temgerw 3:? 1 .13 Ifibs; Lbs b lbsey 1 m libs. mm gb tz .I bs. l F

0- es- 0-. .es- 0-1 'es: -0-1Tes vent in Eto vent in vent in. z went; t

Starting Mix solubility First Stage Resin to M0. 11018111181710 1 10a 85 20- in--- 10. 20. 75 3 .820? 2. 51? 90 (l 73% 8.2851515 22117.11 ,100 150 Ex. No. 1541)..." 1

Second Stage i Slight tend- Resin to Et0 I I. ,-encm:tov 2.27 8.28215.85':11.771 3.82 7.33? 5.453 4.46} 8.52i 6.331 100;:1; 182- 'tatdibi- 'EX'. N0;t155D Third Stage Resin to EtO Molal Ratio 1:10. Ex. No.156b

Fourth Stage MolalRatio 1:15. Ex. N0. 157b.- 1

Fifth Stage Resin to EtO-.

Molal Ratio 1'20 Ex. Not158b 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING A NUCLEAR HYDROGENATED HYDROPHILE OXYALKYLATED 2,4,6 C4-TO C12-HYDROCARBON SUBSTITUTED MONOCYCLIC PHENOL-C1- TO C8-ALDEHYDE RESIN IN WHICH THE RATIO OF OXYALKYLENE GROUPS TO PHENOLIC NULCEI IS AT LEAST 2:1 AND THE ALKYLENE RADICALS OF THE OXYALKYLENE GROUPS ARE SELECTED FROM THE CLASS CONSISTING OF ETHYLENE, PROPYLENE, BUTYLENE, HYDROXYPROPYLENE AND HYDROXYBUTYLENE RADICALS, AND WITH THE PROVISO THAT THE HYDROPHILE PROPERTIES OF SAID OXYALKYLATED RESIN IN AN EQUAL WEIGHT OF XYLENE ARE SUFFICIENT TO PRODUCE AN EMULSION WHEN SAID XYLENE SOLUTION IS SHAKEN VIGOROUSLY WITH ONE TO THREE VOLUMES OF WATER. 